Paczkowski, Nicola S. (Loveland, OH, US)
Winter, Andreas (Neuleiningen, DE)
Langhauser, Franz (Ruppertsberg, DE)

Plaque It! Sponsored by: Flash of Genius

11/001272

01/30/2007

12/01/2004

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Novolen Technology Holdings, C.V. (The Hague, NL)

526/129

526/165, 502/110, 502/120, 502/152

C08F4/02; C08F4/6392

502/120, 526/943, 526/129, 502/152, 502/110, 502/104, 526/165

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Lu, Caixia

Dilworth & Barrese, LLP

What is claimed is:

1. A process for the preparation of a catalyst system, comprising the steps of: a) combining a support material with a first composition, the first composition comprising a first portion of at least one aluminoxane or mixtures thereof in a first solvent, wherein the first composition contains at least 5 mmole of the aluminoxane per gram of the support material; b) heating the combined support material with the first composition to a temperature of from at least 30° C. to about 200° C. to provide an aluminoxane loaded support; and, c) contacting the aluminoxane loaded support with a second composition, the second composition comprising at least one metallocene compound, a second solvent, and a cocatalyst, wherein the cocatalyst includes a second portion of at least one aluminoxane, alone or in combination with an ionic compound and/or a Lewis acid.

2. The process of claim 1 wherein the heating step (b) is performed at a temperature of from at least 50° C. to about 160° C.

3. The process of claim 1 wherein the heating step (b) is performed at a temperature of from at least 80° C. to about 140° C.

4. The process of claim 1 wherein the support material is treated to acheive a loss on dryness of less than 0.5 wt% before performing step a).

5. The process of claim 1 wherein the first composition is further defined in that it contains at least about 7 mmoles of the aluminoxane per gram of support material.

6. The process of claim 1 wherein the first composition is further defined in that it contains at least about 10 mmoles of the aluminoxane per gram of support material.

7. The process of claim 1 wherein the first solvent comprises at least one compound selected from the group consisting of pentane, hexane, isohexane, heptane, toluene and xylene.

8. The process of claim 1 wherein the support material is a silica support, the aluminoxane is methylaluminoxane and the first solvent is toluene, and wherein the silica support and the first composition are contacted at a temperature of from about 10° C. to less than 30° C. and kept at said temperature for up to about 12 hours, and wherein heating step (b) is subsequently performed at a temperature of at least 30° C. for from about 30 minutes to about 20 hours.

9. The process of claim 1 wherein the support material is a silica support, the aluminoxane is methylaluminoxane and the first solvent is toluene, and wherein the silica support and the first composition are contacted at a temperature of about 18° C. to 22° C. and kept at said temperature for from about 0.15 hours to about 2 hours, and wherein heating step (b) is subsequently performed at a temperature of at least 30° C. for from about 1 to about 6 hours.

10. The process of claim 1 wherein the support material is a silica support, the aluminoxane is methylaluminoxane and the first solvent is toluene, and wherein the silica support and the first composition are contacted at a temperature of about 18° C. to 22° C. and kept at said temperature for from about 0.15 hours to about 2 hours, and wherein heating step (b) is subsequently performed at a temperature of at least 50° C. for from about 1 to about 6 hours.

11. The process of claim 1 wherein the support material is a silica support, the aluminoxane is methylaluminoxane and the first solvent is toluene, and wherein the silica support and the first composition are contacted at a temperature of about 18° C. to 22° C. and kept at said temperature for from about 0.15 hours to about 2 hours, and wherein heating step (b) is subsequently performed at a temperature of at least 80° C. for from about 1 to about 6 hours.

12. The process of claim 1 wherein the support material is a silica support, the aluminoxane is methylaluminoxane and the first solvent is toluene, and wherein the silica support and the first composition are contacted at a temperature of about 18° C. to 22° C. and kept at said temperature for from about 0.15 hours to about 2 hours, and wherein heating step (b) is subsequently performed at a temperature of at least 110° C. for from about 1 to about 6 hours.

13. The process of claim 1 wherein the contacting step (c) is performed at a temperature between 0° C. to 100° C. for 1 minute to 200 hours.

14. The process of claim 1 wherein the contacting step (c) is performed at a temperature between 20° C. to 30° C. for 1 mm to 200 hours.

15. The process of claim 1 wherein in contacting step (c) the second composition contains at least about 0.5 mmole of the at least one aluminoxane or mixture of aluminoxanes per gram of the support material.

16. The process of claim 1 wherein in contacting step (c) the second composition contains at least about 1.0 mmole of the at least one aluminoxane or mixture of aluminoxanes per gram of the support material.

17. The process of claim 1 wherein in contacting step (c) the aluminoxane loaded support is contacted with the second composition for a period of time of from about 1 minute to about 24 hours.

18. The process of claim 1 wherein in contacting step (c) the aluminoxane loaded support is contacted with the second composition for a period of time of from about 5 minutes to 6 hours.

19. The process of claim 1 wherein contacting step (c) comprises passing the second composition through the aluminoxane loaded support material in a direct flow.

20. The process of claim 1 wherein in contacting step (c) the total volume of the second composition does not exceed 250% of the pore volume of the support material.

21. The process of claim 1 wherein the total amount of aluminoxane used in steps (a) and (c) together is between 6 mmoles and 24 mmoles of aluminoxane per gram of support material.

22. The process of claim 1 wherein the total amount of aluminoxane used in steps (a) and (c) together is between 8 mmoles and 20 mmoles of aluminoxane per gram of support material.

23. The process of claim 1 wherein the total amount of aluminoxane used in steps (a) and (c) together is between 11 mmoles and 18 mmoles of aluminoxane per gram of support material.

24. A process of claim 1 wherein the amount of metallocene compound used is between 0.1 mol% and 1.7 mol% of aluminoxane per gram of support material.

25. The process of claim claim 1 wherein the at least one aluminoxane includes a compound having the formula
(R-AL-O)_p wherein R includes one or more groups selected from alkyl groups having from 1 to about 10 carbon atoms, an aryl group having from 6 to about 18 carbon atoms, benzyl, or hydrogen, and p is an integer of from 2 to about 50.

26. The process of claim 25 wherein R is either methyl, ethyl, isobutyl, n-butyl, phenyl or benzyl.

27. The process of claim 25 wherein R includes at least about 60% methyl radicals and from about 0.01% to about 40% of either hydrogen, isobutyl or n-butyl radicals, based upon the total number of R radicals.

28. The process of claim 25 wherein the at least one aluminoxane includes a compound having the formula wherein R includes one or more groups selected from alkyl groups having from 1 to about 10 carbon atoms, an aryl group having from 6 to about 18 carbon atoms, benzyl, or hydrogen, and p is an integer of from 2 to about 50.

29. The process of claim 28 wherein R is either methyl, ethyl, isobutyl, n-butyl, phenyl or benzyl.

30. The process of claim 28 wherein R includes at least about 60% methyl radicals and from about 0.01% to about 40% of either hydrogen, isobutyl or n-butyl radicals, based upon the total number of R radicals.

31. The process of claim 1 wherein the at least one aluminoxane includes a compound having the formula wherein R includes one or more groups selected from alkyl groups having from 1 to about 10 carbon atoms, an aryl group having from 6 to about 18 carbon atoms, benzyl, or hydrogen, and p is an integer of from 2 to about 50.

32. The process of claim 31 wherein R is either methyl, ethyl, isobutyl, n-butyl, phenyl or benzyl.

33. The process of claim 31 wherein R includes at least about 60% methyl radicals and from about 0.01% to about 40% of either hydrogen, isobutyl or n-butyl radicals, based upon the total number of R radicals.

34. The process of claim 1 wherein the at least one aluminoxane includes a compound having the formula wherein R includes one or more groups selected from alkyl groups having from 1 to about 10 carbon atoms, an aryl group having from 6 to about 18 carbon atoms, benzyl, or hydrogen, and p is an integer of from 2 to about 50.

35. The process of claim 34 wherein R is either methyl, ethyl, isobutyl, n-butyl, phenyl or benzyl.

36. The process of claim 34 wherein R includes at least about 60% methyl radicals and from about 0.01% to about 40% of either hydrogen, isobutyl or n-butyl radicals, based upon the total number of R radicals.

37. The process of claim 1 wherein the first solvent and second solvent are hydrocarbon compounds.

38. The process of claim 37 wherein the first solvent and second solvent are individually selected from the group consisting of pentane, isopentane, hexane, isohexane, heptane, octane, nonane, cyclopentane, cyclohexane, benzene, toluene, ethylbenzene and diethylbenzene.

39. The process of claim 1 wherein the support material comprises a particulate porous solid selected from the group consisting of inorganic compounds and finely divided polymer powder.

40. The process of claim 39 wherein the support material comprises a particulate inorganic compound selected from the group consisting of silicon dioxide, aluminum oxide, aluminosilicates, zeolites, MgO, ZrO₂ TiO₂, B₂O₃, CaO, ZnO, ThO₂, Na₂O, K₂O, Li₂O, mixed aluminum and silicon oxides, mixed magnesium aluminum oxides, mixed aluminum magnesium oxides, Na₂CO₃, K₂CO₃, CaCO₃, MgCl₂, Na₂SO₄, Al₂(SO₄)₃ BaSO₄, KNO₃, Mg(NO₃)₂ and Al(NO₃)₃.

41. The process of claim 1 wherein the support material is silica.

42. The process of claim 1 wherein the support material is thermally pretreated at a temperature of from about 80° C. to about 1000° C. in an inert gas atmosphere for from about 1 to about 24 hours.

43. The process of claim 1 wherein the support material is thermally pretreated at a temperature of from about 150° C. to about 400° C. in an inert gas atmosphere for from about 1 to about 24 hours.

44. The process of claim 1 for preparing a supported catalyst system wherein the support material is silica with a loss on ignition of 1 wt% or greater.

45. The process of claim 1 for preparing a supported catalyst system wherein the support material is silica with a loss on ignition between 1.5 and 3.5 wt.%.

46. The process of claim 1 wherein the metallocene compound has the formula (1):
(R⁹)_n(L¹)_mM¹(R¹)_q (1) where n is 0 or 1, m is 1, 2 or 3 q is 1, 2 or 3 and the sum of m and q equals the oxidation state of M¹ L¹ are identical or different and are each a substituted or unsubstituted mononuclear or polynuclear hydrocarbon radical or (a) hetero atom(s) containing hydrocarbon radical(s) that coordinates to M¹, R¹ are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from about 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, and two or three R¹ can form one or more ring system(s), M¹ is a metal of group IVb of the Periodic Table of the Elements, R⁹ is a bridging group linking two ligands L¹ selected from where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical or different and are each a hydrogen atom, a C₁–C₄₀ group selected from an alkyl group having from 1 to about 30 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms, wherein R⁴⁰ and R⁴¹ together with the atoms connecting them can form one or more cyclic systems or R⁴⁰ and/or R⁴¹ can contain additional hetero atoms selected from Si, B, Al, O, S, N, P, Cl and Br, x is an integer from 1 to 18, M¹² is silicon, germanium or tin, and R⁹ can link two units of the formula 1 to one another, or R⁹ forms a R⁹-Z¹ group, with R⁹ being linked to one L¹ group and Z¹ being linked to M¹, where Z¹ comprises nitrogen, phosphorus, oxygen or sulfur such as —O—, —S—, —NR⁴² or PR⁴²—, where R⁴² is a hydrogen atom, a C₁–C₄₀ group such as an alkyl group having from 1 to about 30 carbon atoms, a cycloalkyl group of from 3 to 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms.

47. The process of claim 46 wherein the L¹ hydrocarbon radicals are selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, azurenyl, fluorenyl, azapentalenyl, thiapentalenyl or oxapentalenyl.

48. The process of claim 1 wherein the metallocene compound has the formula 1a:
R⁹L¹L²M¹R¹R² (1a) where L¹ and L² are identical or different and are each a substituted mononuclear or polynuclear hydrocarbon radical or (a) hetero atom(s) containing hydrocarbon radical(s) which can form a sandwich structure with the central atom M¹, R¹ and R² are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from about 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, and R¹ and R² can form one or more ring system(s), M¹ is a metal of group IVb of the Periodic Table of the Elements, R⁹ is a bridge between the ligands L¹ and L², where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical or different and are each a hydrogen atom, a C₁–C₄₀ group such as an alkyl group having from 1 to about 30 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms. R⁴⁰ and R⁴¹ together with the atoms connecting them can form one or more cyclic systems or R⁴⁰ and/or R⁴¹ can contain additional hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, Cl and Br, x is an integer from 1 to 18, M¹² is silicon, germanium or tin, and R⁹ may also link two units of the formula (1a) to one another.

49. The process of claim 48 wherein: M¹ is zirconium or hafnium, L1 and L2 are identical or different and are each a substituted cyclopentadienyl, indenyl, tetrahydroindenyl, azurenyl, fluorenyl, azapentalenyl, thiapentalenyl or oxapentalenyl, which can form a sandwich structure with the central atom M¹, R⁹ is R⁴⁰R⁴¹Si═, R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ are identical or different and are each a hydrogen atom, a hydrocarbon group of from 1 to about 30 carbon atoms, in particular an alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms, an alkylaryl group of from 7 to about 14 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl or an arylsilyl group.

50. The process of claim 48 wherein M¹ is zirconium and L¹ and L² are identical or different and are each a substituted indenyl, azurenyl, fluorenyl, azapentalenyl, thiapentalenyl or oxapentalenyl, which can form a sandwich structure with the central atom M¹, and the bridging unit R⁹ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclo-pentyl, cyclo-pentadienyl, cyclohexyl, phenyl, benzyl, trimethylsilyl or 3,3,3-trifluoropropyl.

51. The process of claim 48 wherein the metallocene compound has formula 1b below: wherein M¹ is a metal of group IVb of the Periodic Table of the Elements, R¹ and R² are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms and R¹ and R² may form one or more ring system(s), R³, R⁴, R⁵, R⁶, R⁷, R⁸ and also R^3′, R^4′, R^5′, R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom, a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or an arylsilyl group, with the proviso that R³ and R^3′ are not hydrogen, wherein said groups may contain one or more hetero atoms selected from the groups consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and two adjacent radicals R⁵, R⁶ or R^5′, R^6′, or R⁶, R⁷ or R^6′, R^7′, or R⁷, R⁸ or R^7′, R^8′ in each case may form a hydrocarbon ring system and the bridging unit R⁹ has the meaning set forth above with respect to formula (1a).

52. The process of claim 51 wherein: M¹ is zirconium or hafnium, R¹ and R² are identical or different and are an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms or a halogen atom, or R¹ and R² together may form one or more ring system(s), R³ and R^3′, are identical or different and are each a linear, cyclic or branched hydrocarbon group which may be halogenated, for example an alkyl group of from 1 to 10 carbon atoms or an alkenyl group of from 2 to about 10 carbon atoms, R⁴, R⁵ R⁶, R⁷, R⁸ and also R^4′, R^5′, R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilyl group, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 10 carbon atoms, which may contain one ore more hetero atoms selected form the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and the two adjacent radicals R⁵, R⁶ and R^5′, R^6′ can form a hydrocarbon ring system, R⁹ is R⁴⁰R⁴¹Si═, R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ are identical or different and are each a hydrogen atom, an alkyl group of from 1 to 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms or an alkylaryl group of from 7 to about 14 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl or an arylsilyl group.

53. The process of claim 51 wherein: M¹ is zirconium, R¹ and R² are identical or different and are methyl, chlorine or phenolate, R³ and R^3′, are identical or different and are each a linear, cyclic or branched hydrocarbon group which may be halogenated, for example an alkyl group of from 1 to about 10 carbon atoms or an alkenyl group of from 2 to about 10 carbon atoms, R⁴ and also R^4′ are hydrogen, R⁵, R⁶, R⁷, R⁸ and also R^5′, R^6′, R^7′, R^8′ are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 10 carbon atoms and/or the two adjacent radicals R⁵, R⁶ and R^5′, R^6′ respectively together may form a ring system, R⁹ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl, benzyl, trimethylsilyl or 3,3,3-trifluoropropyl.

54. The process of claim 48 wherein the metallocene compound has formula 1c: where the substituents and indices have the following meanings: M¹ is a metal of group IVb of the Periodic Table of the Elements, R¹ and R² are identical or different and are each a hydrogen atom, an alkyl group of from 1 to 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, and R¹ and R² may form one or more ring system(s), R³, R⁴, R⁵, R⁶, R⁷, R⁸ and also R^3′, R^4′, R^5′, R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom, a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 1 to 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arenyl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an arylakenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, with the proviso that R³ and R^3′ are not hydrogen and that R⁵ and R^5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms, the hydrocarbon groups may contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and the bridging unit R⁹ has the meaning set forth above with respect to formula 1a.

55. The process of claim 54 wherein: M¹ is zirconium or hafnium, R¹ and R² are identical or different and are an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, or a halogen atom, and R¹ and R² may form one or more ring system(s), R³ and R^3′, are identical or different and are each a linear, cyclic or branched group which may be halogenated, for example an alkyl group of from 1 to about 10 carbon atoms or an alkenyl group of from 2 to about 10 carbon atoms, R⁴, R⁶, R⁷, R⁸ and also R^4′, R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, which may contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, R⁵ and R^5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms, R⁹ is R⁴⁰R⁴¹Si═, R⁴⁰R⁴¹Ge═, R R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ are identical or different and are each a hydrogen atom, a C₁–C₃₀-hydrocarbon group, in particular an alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms, an alkylaryl group of from 7 to about 14 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl or an arylsilyl group.

56. The process of claim 54 wherein: M¹ is zirconium, R¹ and R² are identical and are methyl, chlorine, or phenolate, R³ and R^3′ are identical or different and are each a linear, cyclic or branched methyl, ethyl, propyl, butyl, pentyl or hexyl, R⁴ and also R^4′ are hydrogen, R⁶, R⁷, R⁸ and also R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, which may contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, R⁵ and R^5′ are identical or different and are phenyl, naphthyl, para-(C₁–C₁₀-alkyl)phenyl, para-(C₁–C₁₀-fluoroalkyl)phenyl, meta-(C₁–C₁₀-alkyl)phenyl, meta-(C₁–C₁₀-alkyl)phenyl, meta, metá-(C₁–C₁₀-alkyl)₂phenyl or meta, metá-(C₁–C₁₀-fluoroalkyl)₂phenyl, R⁹ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl, benzyl, trimethylsilyl or 3,3,3-trifluoropropyl.

57. The process of claim 48 wherein the metallocene compound has the formula 1d: wherein: M¹ is a metal of group IVb of the Periodic Table of the Elements, R¹ and R² are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to 20 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 14 carbon atoms, or R¹ and R² together may form one or more ring system(s), R⁴, R⁵, R⁶, R⁷, R⁸ and also R^4′, R^5′, R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom, a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, with the proviso that R⁵ and R^5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms, the hydrocarbon groups can contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, R³ is a hydrocarbon group, not cyclic or branched in the α-position, for example an alkyl group of from 1 to 20 carbon atoms, an aryl substituted alkyl group of from 7 to about 40 carbon atoms, or an aryl substituted alkenyl group of from 8 to about 40 carbon atoms, the hydrocarbon groups can contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, R^3′ is a in α-position or in β-position cyclic or branched hydrocarbon group, for example an alkyl group of from 3 to about 20 carbon atoms, an alkenyl group of from 3 to about 20 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms or an arylalkenyl group of from 8 to about 40 carbon atoms, the hydrocarbon groups may contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and the bridging unit R⁹ has the meaning mentioned above with respect to formula 1a.

58. The process of claim 57 wherein: M¹ is zirconium or hafnium, R¹ and R² are identical or different and are an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms or a halogen atom, and R¹ and R² may form one or more ring system(s), R³ is a linear alkyl group of from 1 to about 10 carbon atoms or an alkenyl group of from 2 to 10 carbon atoms, which can be halogenated, R^3′ is a in α-position or in β-position cyclic or branched alkyl group of from 3 to about 20 carbon atoms, an alkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, or a trimethylsilyl group, R⁴, R⁶, R⁷, R⁸ and also R^4′, R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, which may contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, R⁵ and R^5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms, like phenyl, naphthyl, para-(C₁–C₁₀-alkyl)phenyl, meta-(C₁–C₁₀-alkyl)phenyl, meta, metá-(C₁–C₁₀-alkyl)₂phenyl, R⁹ is R⁴R⁴¹Si═, R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ are identical or different and are each a hydrogen atom, a C₁–C₃₀ group, in particular an alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to 14 carbon atoms, an alkylaryl group of from 7 to 14 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl or an arylsilyl group.

59. The process of claim 57 wherein: M¹ is zirconium, R¹ and R² are identical and are methyl, chlorine, or phenolate, R³ is methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl, R^3′ is iso-propyl, iso-butyl, n-butyl, sec-butyl, cyclobutyl, 1-methyl-butyl, 1-ethyl-butyl, 1-methyl-pentyl, cyclopentyl, cyclohexyl, cyclopent-2-enyl, cyclopent-3-enyl, cyclohex-2-enyl, cyclohex-3-enyl, para-methyl-cyclohexyl or trimethylsilyl, R⁴ and also R^4′ are hydrogen, and R⁶, R⁷, R⁸ and also R^6′, R^7′ and R^8′ are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, which may contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, R⁵ and R^5′ are identical or different and are phenyl, p-isopropyl-phenyl, p-tert.-butyl-phenyl, p-s-butyl-phenyl, p-cyclohexyl, p-trimethylsilyl-phenyl, p-adamantyl-phenyl, p-(trisfluor)trimethyl-phenyl or m,m′-dimethyl-phenyl, R⁹ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclo-pentyl, cyclo-pentadienyl, cyclohexyl, phenyl, benzyl, trimethylsilyl or 3,3,3-trifluoropropyl.

60. The process of claim 1 wherein the at least one metallocene compound is selected from the group consisting of: A-(2-isopropyl-4-(p-isopropyl-phenyl)indenyl)(2-methyl-4-(p-isopropyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2-methyl-4-(p-tert. butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2,7-dimethyl-4-(p-tert. butyl-phenyl)indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-(p-tert. butyl-phenyl)indenyl)zirconiumdichloride, A-(2-isopropyl-6-methyl-4-(p-tert. butyl-phenyl)indenyl)(2,6-dimethyl-4-(p-tert. butyl-phenyl)indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-sec. butyl-phenyl)indenyl)(2-methyl-4-(p-sec. butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-cyclohexyl-phenyl)indenyl)(2-methyl-4-(p-cyclohexyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-trimethylsilyl-phenyl)indenyl)(2-methyl-4-(p-trimethylsilyl-phenyl)indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-adamantyl-phenyl)indenyl)(2-methyl-4-(p-adamantyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)(2-methyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)zirconiumdichloride, A-(2-isopropyl-4-phenyl-indenyl)(2-methyl-4-(p-tert. butyl-phenyl)indenyl)-zirconiumdichloride; A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2-methyl-4-phenyl-indenyl)-zirconiumdichloride, A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2,7-dimethyl-4-phenyl-indenyl)-zirconiumdichloride, A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-isopropyl-6-methyl-4-(p-tert. butyl-phenyl)indenyl )(2,6-dimethyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-isopropyl-4-phenyl-indenyl)(2,7-dimethyl-4-(p-tert. butyl-phenyl)indenyl)-zirconiumdichloride, A-(2-isopropyl-4-phenyl-indenyl)(2,5,6,7-tetramethyl-4-(p-tert. butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-6-methyl-4-phenyl-indenyl)(2,6-dimethyl-4-(p-tert. butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(p-tert. butyl-phenyl)indenyl)(2-methyl-4-(4-naphthyl)-indenyl)-indenyl)zirconiumdichloride, A-(2-isopropyl-4-(4-naphthyl)-indenyl)indenyl )(2-methyl-4-(p-tert. butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(4-naphthyl-indenyl)zirconiumdichloride, A-bis(2-methyl-benzo-indenyl)zirconiumdichloride A-bis(2-methyl-indenyl )zirconiumdichloride, A-bis(2-methyl-4-(1-naphthyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(2-naphthyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4-t-butyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4-isopropyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4-ethyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4-acenaphth-indenyl)zirconiumdichloride, A-bis(2,4-dimethyl-indenyl)zirconiumdichloride, A-bis(2-ethyl-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-ethyl-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-phenyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4,6-diisopropyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4,5-diisopropyl-indenyl)zirconiumdichloride, A-bis(2,4,6-trimethyl-indenyl)zirconiumdichloride, A-bis(2,5,6-trimethyl-indenyl)zirconiumdichloride, A-bis(2,4,7-trimethyl-indenyl)zirconiumdichloride, A-bis(2-methyl-5-isobutyl-indenyl)zirconiumdichloride, A-bis(2-methyl-5-t-butyl-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(tert-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4-methoxy-phenyl)-indenyl )zirconiumdichloride, A-bis(2-ethyl-4-(4-tert-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4-methoxy-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4-tert-butyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-methyl-4-(4-methyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-methyl-4-(4-ethyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-methyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-methyl-4-(4-methoxy-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-ethyl-4-(4-tert-butyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-ethyl-4-(4-methyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-ethyl-4-(4-ethyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-ethyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-ethyl-4-(4-methoxy-phenyl)-indenyl)zirconiumdimethyl, A-bis(2-isopropyl-4-(tert-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4-methoxy-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)hafniumdichloride, A-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)titaniumdichloride, A-bis(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-n-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-n-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-pentyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-tert.-butyl-phenyl)-indenyl)hafniumdichloride, A-bis(2-methyl-4-(4′-tert.-butyl-phenyl)-indenyl)titaniumdichloride, A-bis(2-methyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-n-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-phenyl-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-n-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-pentyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-ethyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-phenyl-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-iso-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-propyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-phenyl-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-n-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-iso-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-n-butyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-phenyl-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-ethyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-n-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-iso-propyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-n-hexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-hexyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdichloride, A-bis(2-methyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumbis(dimethylamine), A-bis(2-ethyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdibenzyl, A-bis(2-methyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumdimethyl, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-5-azapentalene)(2-methyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-6-azapentalene)(2-methyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-ethyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-(4′-n-propyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-isopropyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-6-azapentalene)(2-methyl-4-(4′-isopropyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4′-isopropyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-6-oxapentalen)(2-methyl-4-(4′-isopropyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-6-azapentalene)(2-methyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-5-thiapentalene)(2-methyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-oxapentalene)(2-methyl-4-(4′-n-butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-(4′-s-butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-oxapentalene)(2-methyl-4-(4′-s-butyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-6-azapentalene)(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-n-pentyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4′-n-pentyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-oxapentalene)(2-methyl-4-(4′-n-pentyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4′-cyclohexyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-5-thiapentalene)(2-methyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4′-adamantyl-phenyl )-indenyl)-zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-(4′-tris(trifluoromethyl)methyl-phenyl)-indenyl)-zirconiumdichloride, A-(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4′-tris(trifluoromethyl)methyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-(4′-tris(trifluoromethyl)methyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methyl-4-(4′-tris(trifluoromethyl)methyl-phenyl)-indenyl)zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-ethyl-4-(4′-tert-butyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-5-azapentalene)(2-n-butyl-4-(4′-tert-butyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)-zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methylindenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-4-azapentalene)(2-methylindenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methylindenyl)zirconiumdichloride, A-(2-methyl-5-thiapentalene)(2-methylindenyl)zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methylindenyl )zirconiumdichloride, A-(2-methyl-4-azapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-5-azapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-6-azapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-4-azapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-5-azapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-6-azapentalene)(indenyl)zirconiumdichloride, A-(2,5-dimethyl-N-phenyl-6-azapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-5-thiapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-6-thiapentalene)(indenyl)zirconiumdichloride, A-(2,5-dimethyl-4-thiapentalene)(indenyl)zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-5-azapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-6-azapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-5-thiapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-4-oxapentalene)(2-methyl-4-phenyl-indenyl)zirconiumdichloride, A-(2-methyl-4-azapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-4-thiapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-5-thiapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-6-thiapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-4-oxapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-5-oxapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-(2-methyl-6-oxapentalene)(2-methyl-4,5-benzo-indenyl)zirconiumdichloride, A-bis(2-methyl-4-azapentalene)zirconiumdichloride, A-bis(2-methyl-N-phenyl-4-azapentalene)zirconiumdichloride, and A-bis(2-methyl-4-thiapentalene)zirconiumdichloride, wherein A is Dimethylsilanediyl, Diethylsilanediyl, Dipropylsilanediyl, Dibutylsilanediyl, Dipentylsilanediyl, Dihexylsilanediyl, Diheptylsilanediyl, Dioctylsilanediyl, Dinonanylsilanediyl, Didecanylsilanediyl, Diundecanylsilanediyl, Didodecanylsilanediyl, Dimethylgermanediyl, Diethylgermanediyl, Dipropylgermanediyl, Dibutylgermanediyl, Dipentylgermanediyl, Dihexylgermanediyl, Diheptylgermanediyl, Dioctylgermanediyl, Dinonanylgermanediyl, Didecanylgermanediyl, Diundecanylgermanediyl or Didodecanylgermanediyl, Hexyl(methyl)germanediyl, Ethyl(methyl)germanediyl, Ethyl(methyl)silanediyl, Propyl(methyl)silanediyl, 3,3,3-trifluoropropyl(methyl)silanediyl, Propyl(ethyl)silanediyl, Butyl(methyl)silanediyl, Butyl(ethyl)silanediyl, Butyl(propyl)silanediyl, Pentyl(methyl)silanediyl, Pentyl(ethyl)silanediyl, Pentyl(propyl)silanediyl, Pentyl(butyl)silanediyl, Hexyl(methyl)silanediyl, Hexyl(ethyl)silanediyl or Hexyl(propyl)silanediyl, Hexyl(butyl)silanediyl or Hexyl(pentyl)silanediyl, including all structural isomers.

61. The process of claim 1 wherein the contacting step (c) is performed in combination with a Lewis acid compound having the formula
M²X¹X²X³ wherein M² is selected from boron, aluminum or gallium, and X¹, X² and X³ are the same or different and are each individually hydrogen, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms, or an alkaryl, aralkyl, halo-alkyl or haloaryl group having 1 to about 10 carbon atoms in the alkyl radical and from 6 to about 20 carbon atoms in the aryl radical, wherein the halogen component can be fluorine, chlorine, bromine or iodine.

62. The process of claim 1 wherein the contacting step (c) is performed in combination with a Lewis acid selected from the group consisting of trimethylaluminium, triethylaluminum, triisobutylaluminum, iisobutylaluminum hydride, tributylaluminum, trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethyl-phenyl)borane, tris(3,5-difluorophenyl)borane and tris(3,4,5-trifluorophenyl)borane.

63. The process of claim 1 wherein the contacting step (c) is performed in combination with an ionic compound which comprises a non-coordinating anion selected from the group consisting of tetrakis (pentafluorophenyl) borate, tetraphenylborate, SbF₆⁻, CF₃SO₃⁻ and ClO₄⁻.

64. A process for preparing a supported catalyst system comprising the steps: a) contacting a support material with a first composition, said first composition comprising a first portion of at least one aluminoxane or mixtures thereof in a first solvent, wherein the first composition contains at least about 5 mmoles of aluminoxane per gram of the support material, at a temperature of about 10° C. to 30° C. followed by keeping the mixture at about 20° C. for 0 to 12 hours, subsequently heating the resulting mixture to a temperature of 30° C. to 200° C. and keeping the mixture at 30° C. to 200° C. for 30 minutes to 20 hours, optionally followed by removing all or part of the first solvent and/or optionally followed by one or more washing step(s) using a solvent to provide an aluminoxane loaded support material; b) suspending and/or dissolving, respectively, at least one metallocene and a second portion of an aluminoxane or of a mixture of aluminoxanes, which may or may not be the same as the first portion of the at least one aluminoxane or of a mixture thereof, or of an ionic compound and/or a Lewis acid in a second solvent, which may or may not be the same as the first solvent, or suspension medium at a temperature of 0 to 100° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 10 to 100° to provide an impregnation solution; c) applying the impregnation solution prepared in step (b) to the aluminoxane loaded support material produced in step (a), at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours to provide a supported catalyst; d) removing the major part of the solvent from the supported catalyst and optionally washing the supported catalyst with a suitable solvent; e) isolating the supported catalyst; and, f) optionally prepolymerizing the resulting supported catalyst with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.

65. A process for preparing a supported catalyst system comprising the steps: a) contacting a support material with a first composition which includes at least 5 mmol of an aluminoxane or of a mixture of aluminoxanes per g support material in a first solvent at a temperature of about 20° C. followed by keeping the mixture at about 20° C. for 0.15 to 2 hours, subsequently heating the resulting mixture to a temperature of 50° C. to 160° C. and keeping the mixture at 50° C. to 160° C. for 1 to 6 hours, optionally followed by removing all or part of the first solvent and/or optionally followed by one or more washing step(s) using a solvent to provide an aluminoxane loaded support material; b) suspending and/or dissolving, respectively, at least one metallocene and at least 0.5 mmole of a second portion of an aluminoxane or of a mixture of aluminoxanes per g support material in a second solvent or suspension medium, where the metallocene is used in an amount of at least 0.1 mol% of the total amount of aluminoxane or mixture of aluminoxane per g support material, at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° to provide an impregnation solution, c) applying the impregnation solution prepared in step (b) to the aluminoxane loaded support material produced in step (a), at a temperature of 10° C. to 100° C. and a contact time of 1 minute to 24 hours to provide a supported catalyst; d) removing the major part of the solvent from the supported catalyst; e) optionally washing the supported catalyst with a suitable solvent, and/or drying the supported catalyst at temperatures of 30° C. to 60° C.; and, f) optionally prepolymerizing the supported catalyst with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.

66. A process for preparing a supported catalyst system comprising the steps: a) contacting an optionally thermally pretreated silica support material with at least 10 mmol of an aluminoxane per g support material in a suitable solvent such as toluene at a temperature of about 20° C. followed by subsequently heating the resulting mixture to a temperature of 80° C. to 140° C. and keeping the mixture at 80° C. to 140° C. for 1 to 6 hours, optionally followed by removing all or part of the suitable solvent such as toluene, and/or optionally followed by one or more washing step(s) using a solvent to provide an aluminoxane loaded support material; b) suspending and/or dissolving, respectively, at least one metallocene and at least 0.5 mmole of a second portion of an aluminoxane per g support material in toluene, where the metallocene is used in an amount of at least 0.1 mol% of the total amount of aluminoxane or mixture of aluminoxane per g support material, at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° to provide an impregnation fluid, c) applying the impregnation fluid prepared in step (b) to the aluminoxane loaded support material produced in step (a), at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours to provide a supported catalyst; d) removing the major part of the toluene from the supported catalyst; e) optionally washing the supported catalyst with a suitable solvent, and/or drying the supported catalyst at temperatures of 30° C. to 60° C.; and, f) optionally prepolymerizing the supported catalyst with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.

67. A process for preparing a supported catalyst system comprising the steps: a) contacting an optionally thermally pretreated silica support material with a weight loss on dryness of 0.5 wt.% or less and a weight loss on ignition of 1.0 wt.% or greater with a first composition which includes at least 10 mmol of methylaluminoxane per gram support material in toluene at a temperature of about 20° C. followed by subsequently heating the resulting mixture to a temperature of 110° C. and keeping the mixture at 110° C. for 1 to 6 hours, optionally followed by removing all or part of the toluene, and/or optionally followed by one or more washing step(s) using a solvent to provide an aluminoxane loaded support material; b) Suspending and/or dissolving, respectively, at least one metallocene and at least 1 mmole of a second portion of methylaluminoxane per g support material in toluene, where the metallocene is used in an amount of at least 0.1 mol% of the total amount of aluminoxane per g support material, at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° to provide an impregnation fluid; c) applying the impregnation fluid prepared in step (b) to the methylaluminoxane loaded support material produced in step (a), by passing the impregnation fluid through the methylaluminoxane loaded support material in a direct flow or by using an incipient wetness impregnation technique, where the volume of the impregnation fluid or the total liquid volume used in the impregnation step, respectively, does not exceed 250% of total pore volume of the support material, at a temperature of 10° C. to 100° C. and a contact time of 1 minute to 24 hours to provide a supported catalyst; d) removing the major part of the toluene from the supported catalyst; e) optionally washing the supported catalyst with a suitable solvent, and/or drying the resulting supported catalyst at temperatures of 30° C. to 60° C.; and, f) optionally prepolymerizing the resulting supported catalyst with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.

68. A process for preparing a supported catalyst system comprising the steps: a) contacting an optionally thermally pretreated silica support material with a weight loss on dryness of 0.3 wt.% or less and a weight loss on ignition between 1.5 and 3.5 wt.%, with at least 10 mmol of methylaluminoxane per gram support material in toluene at a temperature of about 20° C. followed by subsequently heating the resulting mixture to a temperature of 110° C. and keeping the mixture at 110° C. for 1 to 6 hours, optionally followed by removing all or part of the toluene, and/or optionally followed by one or more washing step(s) using a solvent to provide an aluminoxane loaded support material; b) suspending and/or dissolving, respectively, at least one metallocene and at least 1 mmole of a second portion of methylaluminoxane per g support material in toluene, where the metallocene is used in an amount of at least 0.1 mol% of the total amount of aluminoxane per g support material, at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° C. to provide an impregnation fluid; c) applying the impregnation fluid prepared in step (b) to the methylaluminoxane loaded support material produced in step (a), by passing the impregnation fluid through the aluminoxane loaded support material in a direct flow or by using an incipient wetness impregnation technique, where the volume of the impregnation suspension or solution or the total liquid volume used in the impregnation step, respectively, does not exceed 250% of the total pore volume of the support material, at a temperature of 10° C. to 100° C. and a contact time of 1 minute to 24 hours to provide a supported catalyst; d) removing the major part of the toluene from the supported catalyst; e) optionally washing the supported catalyst with a suitable solvent, and/or drying the supported catalyst at a temperature of from about 30° C. to 60° C.; and, f) optionally prepolymerizing the supported catalyst with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.

69. A process for the polymerization of olefins comprising: a) preparing a catalyst system in accordance with the process of claim 1; and, b) contacting one or more olefins each having from about 2 to about 20 carbon atoms under polymerization reaction conditions with the catalyst system prepared in accordance with the process of claim 1.

70. The process of claim 69 wherein at least one olefin is a 1-olefin.

71. The process of claim 69 wherein at least one olefin has the formula
R^m—CH═CH—Rⁿ wherein R^m and Rⁿ can be identical or different and are each individually a hydrogen atom or a radical having from 1 to about 20 carbon atoms or R^m and Rⁿ together can form one or more rings.

72. The process of claim 69 wherein the olefins include ethylene and one or more 1-olefins having from 4 to about 20 carbon atoms.

73. The process of claim 69 wherein the olefins include propylene.

74. The process of claim 69 wherein the olefins include propylene and ethylene.

75. The process of claim 4 wherein the support material is treated to acheive a loss on dryness of about 0.3% or less before performing step a).

76. The process of claim 64 wherein the support material is treated to achieve a loss on dryness of less than 0.5% before performing step (a).

77. The process of claim 65 wherein the support material is treated to achieve a loss on dryness of less than 0.5% before performing step (a).

78. The process of claim 66 wherein the support material is treated to achieve a loss on dryness of less than 0.5% before performing step (a).

BACKGROUND

1. Field of the Invention

The present invention relates to highly active supported catalyst systems comprising metallocene(s) and cocatalyst(s) such as alumoxane(s), which can advantageously be used in olefin polymerization and to a process for the economical preparation of such catalyst systems, to a process using such catalyst systems for the polymerization and copolymerization of olefins and to polymers which are prepared using such catalyst systems.

2. Background of the Art

Metallocenes may be used as catalyst components for the polymerization and copolymerization of olefins, possibly in combination with one or more cocatalysts. In particular, halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane, to polymerization-active cationic metallocene complexes (EP 0 129 368, EP 0 284 708 or EP 0 302 424).

The synthesis of such metallocenes is well known (U.S. Pat. Nos. 4,752,597; 5,017,714; 5,391,790; 5,616,747 or EP Patent Nos. 0 320 762; 0 416 815; 0 537 686 and 0 669 340). They may be produced, for example, by reacting cyclopentadienyl metal compounds with halides of transition metals, such as titanium, zirconium, and hafnium.

It is also well known that basic properties of the metallocenes, such as polymerization activity, stereoselectivity, regioselectivity, and maximum achievable polymer molecular weight can be systematically controlled by specific substitution patterns of the ligand sphere. However, to use metallocenes for the stereoselective and regioselective polymerization of olefins, the preparation of the isomerically pure racemic form is absolutely necessary, since the corresponding meso form produces undesired atactic polymer, like atactic polypropylene. The isomerically pure racemic form is understood to mean a rac:meso ratio of at least 5, and preferably 10.

Such stereoselective and/or regioselective metallocenes for the polymerization of olefins to polyolefins especially for the polymerization of propylene or the copolymerization of propylene with other olefins and which are useful and preferred as metallocenes for the catalyst systems of the present invention, are well known in the literature. As an example, such metallocenes are disclosed in U.S. Pat. Nos. 4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,931,417; 4,933,403; 4,937,299; 5,017,714; 5,026,798; 5,057,475; 5,120,867; 5,132,381; 5,145,819; 5,155,180; 5,198,401; 5,239,022; 5,243,001; 5,276,208; 5,278,119; 5,296,434; 5,304,614; 5,324,800; 5,328,969; 5,329,033; 5,350,723; 5,374,752; 5,391,790; 5,416,178; 5,436,305; 5,455,366; 5,510,502; 5,532,396; 5,543,373; 5,554,704; 5,576,260; 5,612,428; 5,616,663; 5,629,254; 5,635,437; 5,661,096; 5,672,668; 5,679,812; 5,723,640; 5,739,366; 5,741,868; 5,770,753; 5,786,432; 5,830,821; 5,840,644; 5,840,948; 5,852,142; 5,929,264; 5,932,669; 6,017,841; 6,051,522; 6,051,727; 6,057,408; 6,087,291; 6,100,214; 6,114,479; 6,117,955; 6,124,230; 6,140,432; 6,194,341; 6,218,558; 6,228,795; 6,242,544; 6,245,706; 6,252,097; 6,255,506; 6,255,515; 6,376,407; 6,376,408; 6,376,409; 6,376,410; 6,376,411; 6,376,412; 6,376,413; 6,376,627; 6,380,120; 6,380,121; 6,380,122; 6,380,123; 6,380,124; 6,380,330; 6,380,331; 6,380,334; 6,399,723; 6,444,606; 6,469,114 and US Application Nos. 2001021755; 20030149199 and EP 576 970; EP 611 773, and WO 97/32906; WO 98/014585; WO 98/22486; WO 00/12565; WO 01/48034; WO 03/045964; WO 03/106470.

Processes for preparing polyolefins using soluble, homogeneous catalyst systems comprising a transition metal component of the metallocene type and a cocatalyst component of the type of an aluminoxane are well known. In polymerizations using such soluble, homogeneous catalyst systems, heavy deposits are formed on reactor walls and the stirrer if the polymer is obtained as a solid. These deposits are formed by agglomeration of the polymer particles whenever metallocene and/or cocatalyst are present in dissolved form in the suspension. The deposits in the reactor systems quickly reach considerable thickness and have a high strength. They prevent heat exchange to the cooling medium and therefore have to be removed regularly. Such homogeneous catalyst systems cannot be used industrially in liquid monomer or in the gas phase.

To avoid deposit formation in the reactor, supported catalyst systems in which the metallocene and/or the aluminum compound serving as cocatalyst is/are fixed on an inorganic support material have been proposed. As an example, in EP-A-0 576 970 or WO 01/48034 metallocenes and corresponding supported catalyst systems are disclosed. Such supported catalyst systems give polymers, in particular polypropylenes, having melting points of up to about 156° C.

A variety of different processes for preparing supported catalysts are known. As described in WO 94/28034 supported metallocene catalysts can, for example, be obtained by mixing a metallocene and aluminoxane containing solution with the support material and removing the solvent in vacuum. The solution volume of the impregnation solution is thereby greater than the pore volume of the support material.

In another process, the metallocene containing solution is mixed with the support material whereby the solution volume of the impregnation is equal or smaller than the pore volume of the support material (WO 94/14856). The solid catalyst can be isolated as a dry powder by removing the solvent under vacuum.

Other supported metallocene catalyst systems are disclosed in WO 98/01481. Here a metallocene is dissolved in a solvent and precipitated by addition of another solvent in which the metallocene compound is only slightly soluble in the presence of the support material. Thereby, the catalyst is immobilized on the surface and within the pores of the support.

Yet another supported metallocene catalyst can be obtained by impregnation of a support material with an impregnation solution comprising the metallocene component, wherein the impregnation solution flows through the support material (WO 00/05277).

In general, the main deficiency of such supported catalyst systems, developed up to now, is their low productivity under industrially relevant polymerization temperatures of from 50° C. to 100° C. As a consequence, the industrial usefulness of these catalysts is questionable as long as the commercial competitiveness against the established Ziegler-Natta titanium catalysts is not reached. As the necessary catalyst components like metallocenes and cocatalysts are in general expensive chemicals, improvements of the competitiveness by reducing the catalyst costs are limited and the only other option is to increase the catalyst productivity.

The object of the present invention is to address this main disadvantage of the state of the art catalyst systems and to provide supported catalyst systems with improved polymerization performance under industrially relevant polymerization conditions at temperatures of from 50° C. to 100° C.

Furthermore, it is an object of the present invention to provide an economical process for preparing supported metallocene catalysts, which is universally applicable e.g. with regard to different metallocene components and which results in catalyst systems with improved catalyst productivities. The resulting supported catalysts should be homogeneously loaded and should lead to good polymer particle morphologies.

Another object of the present invention is to provide supported metallocene catalysts obtained by the above described process and to provide an environmentally friendly and economical process for preparing polyolefins under industrially relevant polymerization conditions using the catalyst systems of this invention.

SUMMARY

A process is provided herein for the preparation of a catalyst system. The process comprises the steps of combining a support material with a first composition which includes at least one aluminoxane in a first solvent to provide an aluminoxane loaded support; and, contacting the aluminoxane loaded support with a second composition which includes at least one metallocene compound, a second solvent, and a cocatalyst, wherein the cocatalyst includes a second portion of at least one aluminoxane alone or in combination with an ionic compound and/or a Lewis acid.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

The objects of the invention are achieved by a certain process for preparing a supported catalyst system comprising at least one metallocene, at least one cocatalyst, at least one support and, if desired, at least one metal compound and further one additive component. According to the present invention, the catalyst system is prepared by combining at least one metallocene, at least one cocatalyst, at least one support and if desired at least one metal compound and one further additive component. More specifically, the catalyst system of the present invention is prepared by combining at least one support material with a first portion of an aluminumoxane or a mixture of aluminoxanes in a suitable solvent at elevated temperatures. In a subsequent impregnation step the aluminoxane loaded support material is brought into contact with the metallocene component and a second portion of the aluminoxane or a mixture of aluminoxanes or an ionic compound and/or a Lewis acid.

As metallocene component of the catalyst system of the present invention, use is made of at least one compound of the formula 1 below. The term metallocene component is thereby understood to be an organic transition metal compound as depicted in formula 1 that bears at least one substituted or unsubstituted cyclopentadienyl group.
(R⁹)_n(L¹)_m M¹(R¹)_q (Formula 1)
where

n is 0 or 1,

m is 1, 2 or 3

q is 1, 2 or 3 and

the sum of m and q equals the oxidation state of M¹

L¹ are identical or different and are each a substituted or unsubstituted mononuclear or polynuclear hydrocarbon radical or (a) hetero atom(s) containing hydrocarbon radical(s), for example substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, azurenyl, fluorenyl, azapentalenyl, thiapentalenyl or oxapentalenyl, that coordinates to M¹,

R¹ are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from about 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, and two or three R¹ can form one or more ring system(s),

M¹ is a metal of group IVb of the Periodic Table of the Elements,

R⁹ is a bridging group linking two ligands L¹ wherein R⁹ is selected from:

where

R⁴⁰ and R⁴¹, even when bearing the same index, can be identical or different and are each a hydrogen atom, a C₁–C₄₀ group such as an alkyl group having from 1 to about 30 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms. R⁴⁰ and R⁴¹ together with the atoms connecting them can form one or more cyclic systems or R⁴⁰ and/or R⁴¹ can contain additional hetero atoms (i.e., non-carbon atoms) like Si, B, Al, O, S, N or P or halogen atoms like Cl or Br,

x is an integer from 1 to 18,

M¹² is silicon, germanium or tin, and

R⁹ may also link two units of the formula 1 to one another,

or R⁹ forms a R⁹-Z¹ group, with R⁹ being linked to one L¹ group and Z¹ being linked to M¹,

where

Z¹ comprises nitrogen, phosphorus, oxygen or sulfur such as —O—, —S—, —NR⁴² or PR⁴²—,

where

R⁴² is a hydrogen atom, a C₁–C₄₀ group such as an alkyl group having from 1 to about 30 carbon atoms, a cycloalkyl group of from 3 to 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms.

As metallocene component of the catalyst system of the present invention, preference is given to use at least one compound of the formula 1a below,
R⁹L¹L²M^{1R1R2 (Formula 1a)}

where

L¹ and L² are identical or different and are each a substituted mononuclear or polynuclear hydrocarbon radical or (a) hetero atom(s) containing hydrocarbon radical(s), for example substituted cyclopentadienyl, indenyl, tetrahydroindenyl, azurenyl, fluorenyl, azapentalenyl, thiapentalenyl or oxapentalenyl, which can form a sandwich structure with the central atom M¹,

R¹ and R² are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from about 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR₂³² group, where R³² is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, and R¹ and R² can form one or more ring system(s),

M¹ is a metal of group IVb of the Periodic Table of the Elements,

R⁹ is a bridge between the ligands L¹ and L², wherein R⁹ is selected from:

where

R⁴⁰ and R⁴¹, even when bearing the same index, can be identical or different and are each a hydrogen atom, a C₁–C₄₀ group such as an alkyl group having from 1 to about 30 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms. R⁴⁰ and R⁴¹ together with the atoms connecting them can form one or more cyclic systems or R⁴